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Publication numberUS4564648 A
Publication typeGrant
Application numberUS 06/652,858
Publication dateJan 14, 1986
Filing dateSep 21, 1984
Priority dateSep 21, 1984
Fee statusLapsed
Also published asCA1230188A1, EP0177730A2, EP0177730A3
Publication number06652858, 652858, US 4564648 A, US 4564648A, US-A-4564648, US4564648 A, US4564648A
InventorsJozef T. Huybrechts, Victor R. Vleminckx
Original AssigneeE. I. Du Pont De Nemours And Company
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Epoxy graft acrylic water-based primer surfaces
US 4564648 A
Abstract
Dispersion of an epoxy ester graft acrylic in water with a total of no more than 5% of organic volatiles and amines. These dispersions can be used in primer compositions for metal substrates having a minimum of organic solvent emissions and which can crosslink at temperatures from 110-200 C., giving a good balance of hardness, flexibility, humidity, corrosion resistance and anti-chipping properties.
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Claims(14)
We claim:
1. A dispersion in water of:
(a) 10-60% of an epoxy ester graft acrylic polymer formed by reacting 5-30% of an epoxy ester polymer formed by reaction of n moles of a difunctional epoxy resin with terminal oxirane groups and a number average molecular weight (Mn) of 300-5,000, n-1 moles of a diacid, and 2 moles of a monofunctional acid to form a reaction product, onto which is grafted 5-30% of an acrylic monomer by using a peroxide or azo initiator, to produce said epoxy ester acrylic polymer with a Mn=1000-50,000 and an acid number of 30-150,
(b) amines being added to an extent equivalent to neutralizing 50-200% of the moles of acid functionality,
(c) organic solvents,
such dispersion having not more than 10% volatile organic solvents plus amines, and
(d) balance water.
2. The dispersion of claim 1 with 5-20% epoxy ester and 10-30% of an acrylic with acid number 60-140 in 50-80% deionized water, having been azeotropically distilled to leave not more than 5% organic volatiles.
3. The dispersion of claim 1 with the epoxy ester formed by reaction of n moles of a difunctional bisphenol A-based epoxy with Mn=300-2000, n-1 moles an aliphatic-based difunctional acid with a total of 4-40 carbon atoms and 2 moles of monofunctional acid having 2-25 carbon atoms.
4. The dispersion of claim 1 with the acrylic graft formed by reaction of alkyl acrylate, alkyl methacrylate, styrene, hydroxyfunctional acrylates and/or methacrylates, acid functional acrylates and/or methacrylates, alkylmaleates and/or fumarates, using 0.01-10% by weight of initiator based on the acrylic content, at 60180 C., with the acrylic having an acid number of 40-120.
5. The dispersion of claim 1 with the epoxy ester-graft acrylic having been neutralized with a tertiary amine which has a boiling point of 60-220 C.
6. The dispersion of claim 1 containing 0-10% of a water soluble organic solvent.
7. The dispersion of claim 1 of which at least 5-15% is epoxy ester, 5-15% is acrylic graft, up to 5% is neutralizing amine plug organic solvent, and 60-80% is deionized water.
8. The dispersion of claim 1 with the epoxy ester and acrylic graft being formed in an aromatic solvent, neutralizing with the amine and the aromatic solvent distilling off.
9. The coating composition comprising
(a) 10-40% of the expoxy ester graft acrylic polymer described in claim 1, including up to 5% neutralizing amines plus organic solvents, and 30-80% of deionized water,
(b) 0-40% of pigments and extenders,
(c) 0-20% of additives and/or reactive diluents, and
(d) 0-30% of a water soluble or dispersable crosslinker.
10. The coating composition of claim 9 wherein the epoxy ester graft acrylic polymer has at least 5-15% epoxy ester, 5-15% acrylic graft, up to 5% is neutralizing amine plus organic solvent, and 60-80% deionized water.
11. The coating composition of claim 9 wherein the additives are water soluble or dispersible linear or branched polyethylene oxides or polypropylene oxides with a Mn=100-2500.
12. The coating composition of claim 9 wherein the water soluble or dispersible crosslinker is a methylated melamine formaldehyde resin.
13. An epoxy ester graft acrylic polymer made in accordance with paragraph (a) of claim 1.
14. A process of making an epoxy ester graft acrylic polymer in accordance with paragraph (a) of claim 1.
Description
BACKGROUND

This invention relates to epoxy ester polymers having acrylic portions grafted thereto. More particularly, it relates to coating compositions containing such polymers.

U.S. Pat. No. 4,302,373--Steinmetz (Nov. 24, 1981) describes water-borne coating compositions of epoxy resin, polymeric acid and tertiary amine, wherein the epoxy functionality is partially capped with a carboxylic acid polymer to form a hydrogel. Coating compositions made therefrom are taught for use in can coatings and for automotive and paper coatings.

An acetic acid-neutralized aqueous polyaminoamido resin made using dimeric fatty acids is disclosed in European Patent Application Publication No. 60581 of Sept. 22, 1982--Guenter et al (Akzo).

Other aqueous epoxy coating compositions also outside the present invention are disclosed in U.S. Pat. Nos. 4,446,258 of May 1, 1984--Chu et al (Mobil Oil), 4,446,260 of May 1, 1984--Woods et al (International Paint), and 4,444,806 of Apr. 24, 1984--Morgan et al (W. R. Grace).

SUMMARY OF THE INVENTION

The present invention provides a dispersion in water, in precentages by weight based on the total dispersion, of:

(a) 10-60% of an epoxy ester graft acrylic polymer formed by reacting 5-30% of an epoxy ester polymer formed by reaction of n moles of a difunctional epoxy resin with terminal oxirane groups and a number average molecular weight (Mn) of 300-5000, n-1 moles of a diacid, and 2 moles of a monofunctional acid to form a reaction product, onto which is grafted 5-30% of an acrylic monomer by using a peroxide or azo initiator, to produce said epoxy ester acrylic polymer with a Mn=1000-50,000 and an acid number of 30-150,

(b) amines being added to an extent equivalent to neutralizing 50-200% of the moles of acid functionality,

(c) organic solvents,

such dispersion having not more than 10% volatile organic solvents plus amines, and

(d) balance water.

The epoxy ester graft acrylic polymers of (a) above, and methods of making them, are different aspects of the invention.

DETAILED DESCRIPTION

The present invention is made possible by a new method of synthesis of an epoxy ester graft acrylic polymer. The process involves the synthesis of a liner epoxy ester formed by reaction at 80-190 C. of an oxirane terminated bisphenol A epoxy resin with aliphatic diacids and monoacids in approximately stoichiometric proportions so that all the oxirane groups and acid groups have reacted. The reaction is done in a minimum amount of an organic solvent, preferably aromatic for ease of stripping, preferably using a small percentage of a tertiary amine as catalyst. In a second stage an acid functional acrylic is grafted onto the epoxy ester using a peroxide or azo initiator. Grafting onto the epoxy ester is believed to go via hydrogen abstraction of activited carbon-hydrogen bonds. In a third stage the acid functionality on the epoxy ester is neutralized with an amine (50-200% neutralization), the polymer is dispersed in deionized water the excess organic solvents are distilled off.

These epoxy ester-acrylic dispersions then contain a minimum of organic solvents, so as to be able to formulate primer compositions, preferably with no more than 5% organic volatiles.

When combined with water soluble or dispersible crosslinkers, like hexamethoxymethylmelamine, pigments and extenders, primer surfacers can be formulated which show good corrosion resistance over bare steel, an excellent balance of hardness, flexibility, anti-chipping properties, good topcoat hold-out and appearance.

These primer surfacers can be baked for 30 min at from 110 C. to 200 C., still retaining their basic properties. The primers can be applied by conventional or electrostatic spraying. To further improvve application and flow properties, rheology control agents and flow agents can be used. Silica or clay pastes are quite successful for rheology control to prevent pinholing and sagging, and water soluble or dispersable linear or branched polyethylene glycols or polypropyleneglycols are efficient for flow properties. The primer surfacers show excellent initial and wet adhesion over bare steel and cathodic electrode-posited primers. Adhesion and hold-out of conventional topcoats (polyester, alkyd, acrylic) is very good over broad temperature ranges. Hold-out is the resistance to interpenetration at the interface between the layers of primer surfacer and topcoat applied in organic solvents.

The following are examples describing manufacture of epoxy ester graft acrylic dispersions. Parts, proportions and percentages are by weight except where indicated otherwise.

EXAMPLE 1

______________________________________Ingredient           Parts    Producer______________________________________Xylene               2.73Pripol 1014 dimerized fatty                2.80     Unichemaacid (Pri)Epon 1001 epoxy resin                9.62     ShellDimethylolpropionic acid (DMPA)                1.304Dimethylcyclohexylamine (DMCA)                0.032Heat at reflux for 3 hours until acidnumber (AN) is below 3.Xylene               1.00Heat at reflux 150-155 C. while addingover 30 min keeping the exotherm under control.Styrene (S)          2.194Methylmethacrylate (MMA)                2.572Butylacrylate (BA)   5.039Hydroxyethylacrylate (HEA)                0.718Acrylic acid (AA)    0.824Trigonox C tert-butylperoxy-                0.128    Akzobenxoate (BPB)Xylene               0.583Mercaptoethanol      0.200Add over 30 min, hold 10 min.Xylene               1.747S                    2.95MMA                  2.572BA                   1.137HEA                  0.93AA                   1.648BPB                  0.384Mercaptoethanol      0.60Add over 90 min, hold 2 hours.Cool down to 90 C.Dimethylethanolamine (DMEA)                3.113Deionized water (DW) 0.911Add - mix 15 min.DW                   10.06Add and heat at reflux, about 100 C.DW                   49.89Add slowly while distilling off allorganics insoluble in DW at reflux.Test results:       solids 37% (measured 2 hours at 125 C.)      Brookfield viscosity measured at      20 RPM 9800 centipoises (cps) =      9800 milliPascal seconds (mPas)      pH 7.75______________________________________
EXAMPLE 2

______________________________________Ingredient       Parts______________________________________Epon 1001        6.59Pri              19.17DMPA             0.893DMCA             0.023Cellosolve acetate            0.577Xylene           0.60Heat at 150-160 C. until AN below 3.Xylene           1Add and bring to refluxS                3.525MMA              3.525BA               4.23HEA              1.128AA               1.692BPB              0.35Mercaptoethanol  0.55Xylene           0.80Add over 2 hours. Reflux 2 hours.DMEA             1.269DW               1.731Add. Mix 15 min.DW               33.519Add 30%, mix, then add remaining 70%while stripping off organics insoluble inDW.Test results:  solids      32%          visc.       8000 mPas          pH          8.1______________________________________
EXAMPLE 3

______________________________________Xylene          1.74Epon 828 epoxy resin           6.13           ShellPri             5.18DMPA            2.414DMCA            0.032Heat at reflux until AN ≦ 3.Xylene          0.50Heat at refluxS               2.792MMA             2.572BA              5.039HEA             0.718AA              0.824BPB             0.128Xylene          0.683Mercaptoethanol 0.100Add over 30 min, hold 10 min.Xylene          1.747S               2.95MMA             2.572BA              1.137HEA             0.930AA              1.648BPB             0.384Mercaptoethanol 0.300Add over 90 min, hold 2 hours.DMEA            3.113DW              0.911Add, mix 15 min.DW              10.06Add and strip off organic volatiles, thenadd:DW              49.89Test results:   solids      30.5           pH          7.8           visc.       9400 cps______________________________________
EXAMPLE 4

______________________________________Xylene          2.75Pri             2.80Epon 1001       9.62DMPA            1.304DMCA            0.032   Heat at reflux for 3 hours until AN ≦ 3.2 Ethylhexanol  8S               1.235BA              5.311AA              0.988HEA             0.618Methanol        1.30   Add and heat at reflux  100 C.Lucidol benzoylperoxide           0.07          AKZOMMA             3.952Mercaptoethanol 0.052-ethylhexanol  0.70   Add, hold 10 min.MMA             4.694S               0.824BA              0.865HEA             0.617AA              1.482Benzoylperoxide 0.35   Add 30% over 15 min.   Add 45% over 50 min.   Add 25% over 80 min.   Hold 30 min.DMEA            3.053   Add, mix 15 min.DW              65.69   Add while stripping off organics   insoluble in DW.Test results: solids    32.1%         visc.     800 cps    mPas         pH        7.8______________________________________

Following are examples describing manufacture of primer surfacer paints or finishes with a content of organic volatiles of no more than 5%.

Following are examples describing manufacture of finishes paints, application and properties:

EXAMPLE 5

______________________________________Resin dispersion of Example 2                 60.93DW                    6.08DMEA                  0.29Surfynol 104 E anti-form/                 1.84    Air Productsanti-cratering agentPluriol P 900 polypropylene oxide                 2.26    BASFmol. wt. 900 (reactivediluent)Cymel 303 hexamethoxymethylmelamine                 4.20    CyanamidAerosil 200 fumed silica                 0.87    DegussaBlanc Fixe barium sulfate                 10.13   SachtlebenAluminum silicate     2.56Titanium dioxide pigment                 6.73Carbon black          0.034Iron oxide            0.145Deionized water       3.941                 100.000______________________________________ Pigment to binder ratio (P/B) = 74.3/100 Binder ratio: 76.5/15.3/8.2:Resin of Example 2/Cymel 303/Pluriol P 900.

The above mixture is ground to a fineness smaller than 15 μm. Next there is added deionized water to obtain a package viscosity of 100 to 150 sec DIN cup 4 at 20 C.

EXAMPLE 6

The procedure of Example 5 was repeated with the exception that the resin dispersion of Example 2 was replaced by resin of Example 1.

EXAMPLE 7

The procedure of Example 5 was repeated with the exception that the melamine resin Cymel 303 was replaced by Cymel 350, another melamine resin.

EXAMPLE 8

The procedure of Example 5 was repeated with the exception that the dimethylethanolamine was replaced by DMAMP 80 (2-dimethylamino-2-methyl-1-propanol) from IMC Co.

EXAMPLE 9

The procedure of Example 5 was repeated with the exception that reactive diluent Pluriol P 900 (polypropylene oxide, molecular weight 900) was replaced by Luphen 1320 from BASF (branched polyethyleneglycol).

EXAMPLE 10

The procedure of Example 5 was repeated with the exception that Aerosil 200 was replaced by Bentone EW bentonite clay from NL Chemicals.

EXAMPLE 11

The procedure of Example 5 was repeated with the exception that the P:B ratio was changed from 74.3/100 to 50/100.

PANEL PREPARATION

The products of Examples 5-11 were reduced with deionized water to a spray viscosity of 20 seconds DIN cup 4 at 20 C. The coating composition obtained was sprayed over a cataphoretic electrocoated panel at a thickness of 35 μm dry film thickness and cured at a temperature of 170 C. for 25 minutes.

The obtained primer film was coated with different topcoats including alkyd/melamine/acrylic/melamine color coat--clear coat resulting in excellent adhesion gloss, flow and DOI. Test results on the coating properties are given in Table I in terms of:

Buckholz hardness: DIN 53153

Erichson flexibility: DIN 53156

Salt spray: DIN 50021. The rust creepage from the scribeline is measured in mm.

All Examples were submitted to the humidity cabinet according to DIN 50017 for 240 hours over bare steel and 480 lhours over electrocoated panels. In neither of the tests did any blistering occur. Good chip resistance was also observed.

              TABLE I______________________________________           Salt spray                     over electrocated                                over bareExample  Buchholz Erichson  panel      steelNo.    Hardness Flexibility                     500 hrs    144 hrs______________________________________5      98.0     5.9 mm    0 mm       3 mm6      85.0     6.5 mm    0 mm       5 mm7      133.0    4.4 mm    0 mm       7 mm8      100.0    5.4 mm    0 mm       6 mm9      107.0    5.5 mm    0 mm       2 mm10     100.0    5.2 mm    0 mm       4 mm11     92.0     6.5 mm    0 mm       4 mm______________________________________
Patent Citations
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Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4851460 *Aug 18, 1987Jul 25, 1989Herberts Gesellschaft Mit Beschrankter HaftungAqueous coating composition, process for its preparation and its use
US5190994 *Feb 27, 1991Mar 2, 1993Akzo N.V.Polymers/Shell-Core/
US5231131 *Dec 24, 1991Jul 27, 1993E. I. Du Pont De Nemours And CompanyPolymerization with cobalt chain transfer agent and mixing
US5290828 *Jun 11, 1993Mar 1, 1994The Glidden CompanyAqueous dispersed acrylic grafted epoxy polyester protective coatings
US5536775 *Nov 4, 1994Jul 16, 1996Sandoz Ltd.Amine curable compositions
US5898045 *Dec 1, 1994Apr 27, 1999Basf Coatings AgNeutralized, free-radical polymerized addition copolymer as clear protective coatings for automobiles with improved acid resistance and scratch resistance, yellowing resistance
US5916639 *Jul 10, 1995Jun 29, 1999Daicel Huels Ltd.Primer composition for powder coating
US6005029 *Feb 10, 1997Dec 21, 1999Dainippon Ink And Chemicals, Inc.Organic composite-plated steel plate and resin composition for coating material used therein
US6034160 *Dec 19, 1995Mar 7, 2000Inchem Corp.Graft polymer of a polyether and addition polymer
US6107392 *Sep 12, 1997Aug 22, 2000E. I. Du Pont De Nemours And CompanyCoating comprising a dispersed graft copolymer having macromonomers attached at a terminal end to a neutralized polymeric backbone having acid groups, crosslinker and carrier; automotive finishes; protective coatings
US6204310 *May 26, 1997Mar 20, 2001Imperial Chemical Industries PlcMixing together as a melt a resin and a crosslinker under extrusion conditions; dispersing the mixture while still molten into the liquid carrier and allowing the molten dispersed mixture to solidify to form particles.
US6444761 *Dec 28, 1999Sep 3, 2002Kimberly-Clark Worldwide, Inc.Water-soluble adhesive compositions
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US20110217558 *Dec 21, 2007Sep 8, 2011Brogan Paul HChemical composition and method of applying same to enhance the adhesive bonding of glass laminates
DE3544337A1 *Dec 14, 1985Jun 19, 1987Hoechst AgPolymerisatdispersionen, verfahren zu ihrer herstellung, sowie deren anwendung als bindemittel
EP0280730A1 *Aug 28, 1987Sep 7, 1988E.I. Du Pont De Nemours And CompanyEpoxy ester urethane graft acrylic water-based primer surfaces
EP0342080A1 *Apr 21, 1989Nov 15, 1989Elf Atochem S.A.Process for manufacturing themoplastic resins reinforced by long fibres
EP0469646A1 *Apr 12, 1991Feb 5, 1992Akzo Nobel N.V.Hybrid polymer, aqueous dispersions and coating composition therefrom
WO1988001628A1 *Aug 28, 1987Mar 10, 1988Du PontEpoxy ester urethane graft acrylic water-based primer surfaces
WO1989001498A1 *Aug 12, 1988Feb 23, 1989Valspar CorpAqueous coating compositions
WO1989005316A1 *Dec 10, 1987Jun 15, 1989Du PontEpoxy ester urethane graft acrylic water-based primer surfaces
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Classifications
U.S. Classification523/423, 525/404, 528/113, 523/414, 523/417, 523/416, 528/112, 523/407
International ClassificationC09D151/00, C08L51/00, C08L51/02, C08G59/42, C08L51/08, C08K5/17, C08L77/00, C08F283/10
Cooperative ClassificationC08F283/10, C08G59/4292
European ClassificationC08F283/10, C08G59/42Y
Legal Events
DateCodeEventDescription
Mar 29, 1994FPExpired due to failure to pay maintenance fee
Effective date: 19930116
Jan 16, 1994LAPSLapse for failure to pay maintenance fees
Aug 17, 1993REMIMaintenance fee reminder mailed
Jun 27, 1989FPAYFee payment
Year of fee payment: 4
Nov 5, 1984ASAssignment
Owner name: E.I. DU PONT DE NEMOURS AND COMPANY INC., A COMPAN
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:HUYBRECHTS, JOZEF T.;VLEMINCKX, VICTOR R.;REEL/FRAME:004324/0165
Effective date: 19840910